The reduction of the tris-(2,2′-bipyridyl) and the tris-(1,10-phenanthroline) complexes of iron(III) by hydroxide ion

Hydrogenase biomimetics with redox-active ligands: Electrocatalytic proton reduction by [Fe2(CO)4(κ2-diamine)(μ-edt)] (diamine = 2,2′-bipy, 1,10-phen)

“…[18][19][20] Thus, 2,2′-bipy can be doubly reduced and both the π-radical monoanion (2,2′-bipy)˙-and the diamagnetic dianion (2,2′-bipy) 2have been crystallographically characterised. [21][22][23][24] Consequently, 2,2′-bipy is able to support metals from across the periodic table [25][26][27][28][29][30][31] and its complexes have numerous applications [18,19,[32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] . For example, [Ru(2,2′bipy) 3 ] 2+ is the most widely studied one-electron photo-redox catalyst and has facilitated significant advances in energy storage, hydrogen and oxygen evolution from water and methane production from carbon dioxide.…”

“…[18,19,[32][33][34][35] Furthermore, the iron complex [Fe (1,10-phen) 3 ] 3+ is widely used as a coordinatively saturated, one-electron oxidant, a redox indicator, and in model compounds of biologically active substances. [36][37][38][39][40][41][42][43][44][45][46] In 2007, Schollhammer and co-workers reported the first example of a [FeFe]-biomimetic diiron complex containing a chelating diamine, namely [Fe 2 (CO) 4 (κ 2 -1,10-phen)(µ-pdt)] (2pdt) (pdt = SCH 2 CH 2 CH 2 S) (Chart 1). [10] Subsequent work showed that this complex protonated upon addition of HBF 4 •Et 2 O to afford the bridging hydride, [Fe 2 (CO) 4 (κ 2 -1,10-phen)(µ-H)(µpdt)][BF 4 ], which displayed poor thermal stability.…”

A kinetic study of the reduction of the octacyanomolybdate(V) ion by the hydroxide ion

“…Similar to the studies of Nord and Wernberg, [9,10] the first step of the mechanism is proposed to be rate determining. This then corresponds to the rate law: The value of k obsd was determined from Fig.…”

“…Nord and Wernberg [9] reported that the rate of reduction of Fe(bipy) 3 3? and Fe(phen) 3 3? is first-order in both [complex] and [OH -].…”

“…The reduction of tris(2,2 bipyridyl) and tris(1,10 phenanthroline) complexes of iron(III) [9] and osmium(III) [10,11] by the hydroxide ion have been reported. Nord and Wernberg [9] reported that the rate of reduction of Fe(bipy) 3 3? and Fe(phen) 3 3?…”